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CN1268154A - Organoaluminum Compounds Immobilized on Organopolysiloxane Gel Particles - Google Patents

Organoaluminum Compounds Immobilized on Organopolysiloxane Gel Particles Download PDF

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Publication number
CN1268154A
CN1268154A CN98808593A CN98808593A CN1268154A CN 1268154 A CN1268154 A CN 1268154A CN 98808593 A CN98808593 A CN 98808593A CN 98808593 A CN98808593 A CN 98808593A CN 1268154 A CN1268154 A CN 1268154A
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general formula
alo
particle
compound
organoaluminum compound
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赫尔穆特·阿尔特
弗兰克·鲍曼
约翰·魏斯
亚历山大·克普尔
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Wacker Chemicals Co Ltd
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Wacker Chemicals Co Ltd
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F10/00—Homopolymers and copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
    • B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
    • B01J31/12—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing organo-metallic compounds or metal hydrides
    • B01J31/123—Organometallic polymers, e.g. comprising C-Si bonds in the main chain or in subunits grafted to the main chain
    • B01J31/124—Silicones or siloxanes or comprising such units
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
    • B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
    • B01J31/12—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing organo-metallic compounds or metal hydrides
    • B01J31/14—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing organo-metallic compounds or metal hydrides of aluminium or boron
    • B01J31/143—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing organo-metallic compounds or metal hydrides of aluminium or boron of aluminium
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
    • B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
    • B01J31/165—Polymer immobilised coordination complexes, e.g. organometallic complexes
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
    • B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
    • B01J31/22—Organic complexes
    • B01J31/2282—Unsaturated compounds used as ligands
    • B01J31/2295—Cyclic compounds, e.g. cyclopentadienyls
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2231/00—Catalytic reactions performed with catalysts classified in B01J31/00
    • B01J2231/10—Polymerisation reactions involving at least dual use catalysts, e.g. for both oligomerisation and polymerisation
    • B01J2231/12—Olefin polymerisation or copolymerisation
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2231/00—Catalytic reactions performed with catalysts classified in B01J31/00
    • B01J2231/20—Olefin oligomerisation or telomerisation
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2231/00—Catalytic reactions performed with catalysts classified in B01J31/00
    • B01J2231/30—Addition reactions at carbon centres, i.e. to either C-C or C-X multiple bonds
    • B01J2231/32—Addition reactions to C=C or C-C triple bonds
    • B01J2231/324—Cyclisations via conversion of C-C multiple to single or less multiple bonds, e.g. cycloadditions
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
    • B01J2531/40—Complexes comprising metals of Group IV (IVA or IVB) as the central metal
    • B01J2531/48—Zirconium
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
    • B01J2531/80—Complexes comprising metals of Group VIII as the central metal
    • B01J2531/84—Metals of the iron group
    • B01J2531/847—Nickel
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F4/00—Polymerisation catalysts
    • C08F4/42—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors
    • C08F4/44—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides
    • C08F4/60—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides together with refractory metals, iron group metals, platinum group metals, manganese, rhenium technetium or compounds thereof
    • C08F4/619—Component covered by group C08F4/60 containing a transition metal-carbon bond
    • C08F4/61912—Component covered by group C08F4/60 containing a transition metal-carbon bond in combination with an organoaluminium compound
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F4/00—Polymerisation catalysts
    • C08F4/42—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors
    • C08F4/44—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides
    • C08F4/60—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides together with refractory metals, iron group metals, platinum group metals, manganese, rhenium technetium or compounds thereof
    • C08F4/619—Component covered by group C08F4/60 containing a transition metal-carbon bond
    • C08F4/6192—Component covered by group C08F4/60 containing a transition metal-carbon bond containing at least one cyclopentadienyl ring, condensed or not, e.g. an indenyl or a fluorenyl ring
    • C08F4/61922—Component covered by group C08F4/60 containing a transition metal-carbon bond containing at least one cyclopentadienyl ring, condensed or not, e.g. an indenyl or a fluorenyl ring containing at least two cyclopentadienyl rings, fused or not

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  • Chemical Kinetics & Catalysis (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Inorganic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Transition And Organic Metals Composition Catalysts For Addition Polymerization (AREA)
  • Polymers With Sulfur, Phosphorus Or Metals In The Main Chain (AREA)
  • Silicon Polymers (AREA)
  • Processes Of Treating Macromolecular Substances (AREA)
  • Manufacturing Of Micro-Capsules (AREA)
  • Compositions Of Macromolecular Compounds (AREA)

Abstract

The present invention relates to particles composed of organopolysiloxane gel particles and an organoaluminum compound fixed to the particles. The particles can be used as cocatalysts for the oligomerization, cyclization or polymerization of olefins with metal compounds of transition groups IV, V, VI and VIII of the periodic Table.

Description

Be fixed on the organo-aluminium compound on the organic polyorganosiloxane gel particulate
The present invention relates to contain the organic polyorganosiloxane gel particulate and be fixed on the particle of the organo-aluminium compound on this particulate and relate to they the preparation method and the metallic compound of their IV, V, VI and VIII subgroups in periodictable as oligomeric, the cyclisation of alkene or the purposes of polymeric cocatalyst.
Controlled hydrolysis by organo-aluminium compound obtains aikyiaiurnirsoxan beta.For example, make water obtain the methylaluminoxane of oligomerization by the controlled hydrolysis of trimethyl aluminium.
Have application widely as cocatalyst in olefin oligomerization, cyclisation or the polymerization of Organoaluminoxy alkane metal catalytic of the metallic compound of IV, V, VI and VIII subgroup in the life cycle table, wherein the Organoaluminoxy alkane of Tian Jiaing is as the activator of catalytically-active metals compound.For example, in US-A-5206401, methylaluminoxane is added in the metallocene compound of the catalytic activity of IV subgroup metal in the periodictable activator as olefinic polymerization.
When implement metal catalytic and during by Organoaluminoxy alkane (for example, using metallocene or half interlayer catalyzer) activatory olefinic polymerization, the problem of existence is a reactor fouling, just in reaction process, reactor wall is by the polyolefin coated that is generated.No longer may control the temperature of reaction process.This fouling finally causes reactor to stop up fully.In large-scale industrial production, this will cause plant downtime and therefore suffer heavy losses.Another problem that the preparation polyolefine exists is resulting product form.When not adding other additive, obtain the fine powdered product.Yet for further industrial processes, this polymkeric substance should be made bigger particle diameter, preferably has the sphere of 0.1-3mm average ball diameter.
Reactor fouling can make the active catalyst center fixation by cocatalyst such as methylaluminoxane (MAO) or ethyl aikyiaiurnirsoxan beta are coated on the silicon gel.For example, this mentions in US-A-4925821.The heterogenize of described cocatalyst be meant actual polymerization activity cationoid reaction center by with the ionic interaction of negatively charged ion Organoaluminoxy alkane by accurate heterogenize.
In a heterogeneous reaction, implement heterogenize; The problem that the terminal point that must accept the difficult control of humidifying problem, long reaction time, incomplete reaction and reaction and react is difficult to measure.In addition, the heterogenize of catalyzer obviously reduces catalytic activity.Equally, the cocatalyst of the olefine reaction of metal catalytic must be with a large amount of excessive interpolations, just add with 1: 1000 to 1: 20000 molar ratio.The ratio of catalytically-active metals and cocatalyst is quite random and can not be accurately set.
The purpose of this invention is to provide the particle that contains organo-aluminium compound, when this particle metallizing thing together is used as cocatalyst, it has high catalytic activity in oligomeric, the cyclisation of alkene or polymerization, wherein can accurately control the used particulate consumption that contains organo-aluminium compound, just the ratio between reactive metal center and the aluminium.
The present invention relates to contain organic polyorganosiloxane gel particulate with 5-200nm diameter and the particle that is fixed on the organo-aluminium compound on this particulate.
After they were made, this novel particle can suspend or be dissolved in all inert organic solvents at least subtly.This particulate size from the 10nm of individual particle up to assembling 500 microns of caking.
This particle is preferably by [organo-siloxane microgel particle part] a[aikyiaiurnirsoxan beta part] b[monomer and oligomeric organo-aluminium compound] cForm, wherein, a is 1-99.9wt.%, and b is that 1-99wt.% and c are 1-10wt.%, but the adding and be 100wt.% of individual component.
A preferably is at most 50wt.%, more preferably is at most 20wt.%.B preferably is at least 10wt.%, more preferably is at least 50wt.%.B preferably is at most 90wt.%.C preferably is at least 0.1wt.%, more preferably is at least 0.5wt.%, and most preferably is at least 2wt.%.C preferably is at most 5wt.%.
Described particulate organopolysiloxane part preferably by
The general formula of 0.5-80wt.% is [R 1 dR 2 3-dSiO 1/2] unit of (1),
The general formula of 0-99.0wt.% is [R 1 eR 2 2-eSiO 2/2] unit of (2),
The general formula of 0-99.5wt.% is [R 1 fR 2 1-fSiO 3/2] (3) the unit and
The general formula of 0-99.5wt.% is [SiO 4/2] unit of (4) forms,
Wherein, R 1Be the unit price C that identical or different and Si-O-C-key connect and optionally contain functional group 1-C 30Alkyl or hydrogen,
R 2Be identical or different connect and optionally contain functional group and go back selectivity by heteroatoms O, the unit price C that N or S are interrupted with the SiC-key 1-C 30Alkyl or hydrogen,
D is 0,1,2,3,
E is 0,1 or 2, and
F is 0 or 1.
Substituent R not 1Example be alkyl, for example methyl, ethyl and propyl group; Cycloalkyl, for example cyclohexyl; And aryl, for example phenyl.
The radicals R that contains functional group 1Example be the halo alkyl, be preferably haloalkyl, for example 3,3, the 3-chloromethyl, the 3-chloropropyl, the 3-bromopropyl, 3,3,3-trifluoro propyl and 5,5,5,4,4,3,3-hexafluoro amyl group, and halogenated aryl, for example adjacent-,-and right-chloro-phenyl-; Contain primary, the alkyl of secondary and tertiary amine, aminoalkyl for example, as the 2-aminoethyl, the 3-aminopropyl, N-(2-aminoethyl)-3-aminopropyl, N-(2-aminoethyl)-3-amino-(2-methyl) propyl group and pyrimidyl, aminoaryl is as aminophenyl; Quaternary ammonium group; The alkyl that contains sulfydryl, for example 2-mercaptoethyl and 3-sulfydryl propyl group; Cyano group alkyl, for example 2-cyano ethyl and 3-cyano group propyl group; The alkyl that contains the allyl acyl group, allyl acyl group alkyl for example is as 3-allyl acyl group propyl group and 3-isobutyryl propyl group; The alkyl that contains hydroxyl, hydroxyalkyl for example is as hydroxypropyl; Have phosphonic acids, phosphonate group and sulfonic alkyl; By heteroatoms O, that N or S are interrupted is saturated and undersaturated, line style and cyclic hydrocarbon group, for example furyl, pyridyl and thiophenyl.
Radicals R 2Be preferably unsubstituted C 1-C 6Alkyl and phenyl, particularly methyl, ethyl or propyl group.
Other main group element, for example boron and aluminium can be connected to R by the Si-O-C key 1Or have an alkyl R of functional group 1And R 2Other Sauerstoffatom on.
Described particulate aikyiaiurnirsoxan beta part preferably by
The general formula of 0.5-99wt.% is [X iR 4 gR 3 2-gAlO 1/2] unit of (5),
The general formula of 0-99wt.% is [X jR 4 hR 3 1-hAlO 2/2] (6) the unit and
The general formula of 0-99wt.% is [AlO 3/2] unit of (7) forms,
Wherein, R 3Be a hydrogen atom, or identical or different and connect and optionally contain the unit price C of functional group with AlC-, SiC-key 1-C 30Alkyl,
R 4Be a hydrogen atom, or identical or different and connect and optionally contain the unit price C of functional group with the Al-O-C-key 1-C 30Alkyl,
X is a halogen atom,
G is 0,1 or 2,
H is 0 or 1,
I is 0,1,2 and 3, and
J is 0,1 or 2.
H and g are preferably 0.
X is preferably a chlorine atom or fluorine atom.
Radicals R 3Example and preferred embodiment be above-mentioned as R 1Alkyl, cycloalkyl and aryl, and halo alkyl.
Particularly, R 3Be a unsubstituted C 1-C 10Alkyl, phenyl or hydrogen, especially methyl, ethyl, propyl group, sec.-propyl, butyl, isobutyl-, hexyl or decyl.
Unsubstituted radicals R 4Example be above-mentioned as R 1Alkyl, cycloalkyl and aryl.
The radicals R that has functional group 4Example be the halo alkyl, for example above-mentioned as R 1Halo alkyl and 1,3-two ketone adducts.
R 4Unsubstituted C preferably 1-C 6Alkyl or phenyl, especially methyl, ethyl or isobutyl-.Described particulate monomer organo-aluminium compound part is preferably by following general formula R 3 3-i-jR 4 I-jAlX j(8), R 5 2AlYR 5YR 5(9), (CH 2) 5Al-YR 5(10), Compound form, wherein, R 5Be C 1-C 30Alkyl,
Y be have unbound electron to and be selected from oxygen, sulphur or NR 6Group,
R 6Be a hydrogen atom or radicals R 5,
S be 3 to 30 integer and
R 3, R 4, X, i and j are with above-mentioned definition.
Described particulate oligomeric cyclic organo-aluminium compound part is preferably by general formula
(R 3AlO 2/2) k(R 4AlO 2/2) 1(XAlO 2/2) m(13), form, wherein, k, l and m are respectively the integer of 3-30, and the k+l+m sum is at least 3, R 3, R 4, X, i and j are with above-mentioned definition.
The oligomeric line style organo-aluminium compound part of described particulate preferably is made up of general formula (14),
R 3 2-q-rR 4 q-rX rAlO-(R 3AlO 2/2) n(R 4AlO 2/2)。
(XAlO 2/2) pAlR 3 2-q-rR 4 Q-rX r(14), wherein, n, o and p are respectively the integer of 0-50, and q and r are respectively 0,1 and 2, R 3, R 4With X with above-mentioned definition.
Radicals R 5Be preferably C 1-C 10Alkyl or phenyl, especially methyl, ethyl, propyl group, sec.-propyl or butyl.
The monomer organo-aluminium compound is preferably and contains C 1-C 10Three organo-aluminium compounds of alkyl, trimethyl aluminium for example, triethyl aluminum, triisobutyl aluminium and three decyl aluminium; Contain C 1-C 10Two organic hydride aluminium of alkyl, for example dimethyl hydrogenation aluminium and didecyl aluminum hydride; Organic dihydro aluminium compound, for example dimethyl aluminum hydride; Two organic halogenation aluminium, for example dimethylaluminum chlorides; Organic dihalide aluminium, for example methylaluminum dichloride; With the organoaluminum sesquihalide, trimethylammonium dichloride two aluminium for example.
Especially preferably contain C 1-C 10Three organic radical aluminum compounds, particularly trimethyl aluminium of alkyl, triethyl aluminum, tri-propyl aluminum, triisopropylaluminiuand, three n-butylaluminum and three decyl aluminium;
Described particle preferably contains the aikyiaiurnirsoxan beta and the unit of its remainder by the general formula (1) of 1-80wt.% of 5wt.% at least, the unit of the general formula of 1-98wt.% (2), the unit of the general formula of 1-99wt.% (3), form with the unit of the general formula (4) of 1-99wt.%, and the unitary summation of general formula (3) and (4) is at least 1wt.%.
Described particle can also include the 0.01-50wt.% with respect to the particle gross weight, is preferably the following monomer aluminium starting material of 10wt.%.
The invention still further relates to the method that preparation contains the organic polyorganosiloxane gel particulate with 5-200nm diameter and is fixed on the organo-aluminium compound on this particulate, the organo-aluminium compound that wherein will be selected from above-mentioned general formula (8)-(13) compound reacts under the situation that the organic polyorganosiloxane gel particulate with 5-200nm diameter exists with the compound that has hydroxyl.
Suitable organic polyorganosiloxane gel particulate preferably is made up of the unit of above-mentioned general formula (1)-(4).For example, the organic polyorganosiloxane gel particulate be poly-methyl-, ethyl-, phenyl-or vinylsiloxane microgel particle.
The specially suitable organic polyorganosiloxane gel particulate for preparing this kind novel particle is mentioned at EP-A-744432.Particularly preferably under 20 ℃ in a kind of hydrocarbon the solubilized organopolysiloxane particles of 5wt.% at least, described hydrocarbon for example is a unsubstituting aromatic hydrocarbon, as toluene, benzene and dimethylbenzene, unsubstituting fat hydrocarbon, as pentane, iso-pentane, Trimethylmethane, hexane and hexanaphthene, be preferably toluene.
Used organopolysiloxane particles can not contain reactive group, as hydroxyl and alkoxyl group, and only comprises alkyl.
Other extremely suitable organopolysiloxane particles is those that introduce at EP-A-744432, and it comprises total amount and surpasses 15wt.% and have one or three radicals R that the Si-C-keys connect 2Above-mentioned general formula (1)-(4) unit and the 3rd the step in do not remove remaining OH or alkyl.
The organo-aluminium compound of spendable general formula (8)-(13) reacts to make aikyiaiurnirsoxan beta with the compound that contains hydroxyl.
Organo-aluminium compound can use with the form of solid, liquid or gas.They preferably use with the form or the solution of liquid.
The monomer organo-aluminium compound of preferred above-mentioned preferred thing as general formula (8)-(13).
If organo-aluminium compound uses with the form of solution, preferred solvent is the hydro carbons of above-mentioned preferred solvent as the organo-siloxane microgel particle.
Preferably dissolved being reacted component then mixes.If desired, described organo-aluminium compound also can directly be dissolved in the organic polyorganosiloxane gel particulate solution.Based on the gross weight of solution, the preferred concentration of organic polyorganosiloxane gel particulate and organo-aluminium compound is 1wt.% at least, is at most 50wt%, preferably is at most 30wt%, especially preferably is at most 20wt.%.
The compound that has a hydroxyl is water preferably, has the C of hydroxyl 1To C 40-hydrocarbon for example primary, the second month in a season and the tertiary alcohol, glycol, triol, phenol and sugar, or has the mineral compound of hydroxyl, as boric acid or aluminium hydroxide.Especially preferably can be with the water of solid, liquid or gas form interpolation, as crystal water, milk sap or microemulsion.
Mol ratio between hydroxyl and organo-aluminium compound is preferably 0.01: 1-10: in 1 the scope.
Stir the preferred down compound that has hydroxyl that adds.This temperature of adding process is preferably-80 ℃ to 250 ℃, more preferably-20 ℃ to 100 ℃, is preferably-40 ℃ to 0 ℃ especially.
This reaction then preferably-80 ℃ to 200 ℃, more preferably-20 ℃ to 100 ℃, proceed in particularly preferably in 0 ℃ to 80 ℃ temperature range.
Reaction can be undertaken by mixing, also can not undertaken by mixing.Preferably reaction soln is mixed.
Reaction times is at several minutes with between one day, preferably between one hour and ten hours, between 5 minutes and 2 hours.The terminal point of reaction can be emitted and determines by no longer including gas.
When a kind of solvent used in reaction, final particle formed a kind of suspension, and it can be used as other reaction or purposes, for example as cocatalyst.
Final particle also can be preferably under atmosphere of inert gases, preferred argon gas and under said temperature, filter, and with a kind of solvent such as hydrocarbon drip washing.
Filter cake can be preferably under high vacuum then, and is for example at room temperature dry.If desired, described cocatalyst also can without further dry and under rare gas element hygrometric state store.
Another procedure of processing is exactly under reduced pressure to remove to desolvate.
The metallic compound that the invention further relates to described particle IV, V, VI or VIII subgroup in periodictable is as oligomeric, the cyclisation or the polymeric cocatalyst of alkene.
In the periodictable metal catalyst of IV, V, VI or VIII subgroup and as the particle of cocatalyst preferably at an inert solvent, particularly a kind of hydrocarbon, unsubstituting aromatic hydrocarbon just, for example toluene, benzene or dimethylbenzene, or a kind of unsubstituted aliphatic hydrocrbon, as being used to prepare fixed and activatory catalyst system in pentane, iso-pentane, Trimethylmethane, hexane or hexanaphthene, the preferred toluene.
Like this, described particle for example be directly be used in by in the resulting suspension of preparation process or with its preferably rare gas element for example the argon gas low suspension, disperse or be partly dissolved in a kind of suitable inert solvent.Suitable inert solvent is above-mentioned hydro carbons.Preferably under agitation particle is mixed with metal catalyst then.Metal catalyst can be suspended, be disperseed, be partly dissolved or be dissolved in a kind of suitable inert solvent for solid-state or quilt, and above-mentioned in this case hydro carbons is preferred.
Particle can carry out under-80 ℃ to 200 ℃ with mixing of metal catalyst.Preferred temperature range is-40 ℃ to 60 ℃, preferred especially 0 ℃ to 30 ℃ temperature range.The temperature of subsequent reaction step is preferred in above-mentioned temperature range.
Mixing can be carried out in reaction process, but this reaction also can be carried out without mixing step.Preferably reaction soln is mixed.Reaction times is preferably 1 minute to one day, is preferably 1 minute to 10 hours, preferred especially 1 minute to 2 hours.
Described fixed and activatory catalyst system and preferably filter down at rare gas element (preferred argon gas) preferably under said temperature, and preferably use for example above-mentioned hydro carbons drip washing of a kind of inert solvent.This chromatic filter cake then under high vacuum, preferably down dry at-50 ℃ to 100 ℃.If desired, described fixed and activatory catalyst system also can without further dry and under rare gas element hygrometric state store.
Ratio between the aluminium in the metal catalyst in metal and the particle can be set at any required value.This ratio can record by ultimate analysis.
The metallic compound that uses is preferably half lamellar compound of subgroup metal in metallocene and the periodictable.This metal compound is for example mentioned in US-A-4925821.The metallic compound that preferably contains the cyclopentadiene ligand.In the metallic compound preferred metal be titanium, zirconium, alum and nickel,
The metallic compound that the invention still further relates to described particle IV, V, VI and VIII subgroup in periodictable is as oligomeric, the cyclisation or the polymeric cocatalyst of alkene.
In the periodictable metallic compound of IV, V, VI and VIII subgroup and as the cocatalyst particle preferably at an inert solvent, particularly a kind of hydrocarbon, unsubstituting aromatic hydrocarbon just, for example toluene, benzene or dimethylbenzene, or a kind of unsubstituted aliphatic hydrocrbon, as being used to prepare fixed and activatory catalyst system in pentane, iso-pentane, Trimethylmethane, hexane or hexanaphthene, the preferred toluene.
It is dry immediately after finishing that the fixed of described particle and the preparation of its metallizing thing and activatory catalyst body tie up to their preparations, not drying just be used for or only after storing any required time (active do not reduce) be used for oligomeric, cyclisation or the polymeric batch process and the continuous processing of alkene.
For the polymerization of alkene, these catalyst systems the time are joined reactor or are added into continuously in beginning with the form that contains solvent or not solvent-laden suspension that is used for gas-phase reaction or sulfuration bed process.The solvent that is suitable for olefinic polymerization is above-mentioned inertia hydro carbons.Treat that polymeric alkene such as amylene itself also can be used as solvent.
In the next step of olefinic polymerization, monomer or monomer mixture (if they also do not contain in solvent) are added with solid, liquid or gas form in batches or continuously or under the situation of copolymerization successively.
According to used catalyst system, suitable alkene example is line style or ring-type C 2-C 30List-1-alkene, for example ethene, propylene, 1-hexene, cyclopentenes, tetrahydrobenzene and norbornylene, and how unsaturated linearity or ring-type C 2-C 30Alkene, 1,3-butadiene for example, isoprene, 1,3-pentadiene, vinylbenzene, alpha-methyl styrene and norbornadiene.Above-mentioned all alkene all can be with any required ratio homopolymerization and copolymerization.
Described reaction can be carried out through mixing step.Temperature of reaction is preferably-80 ℃ to 200 ℃, more preferably 0 ℃ to 140 ℃, preferred especially 60 ℃ to 120 ℃.Pressure in the reaction process can be preferably 1 crust to 400 crust.
Products therefrom can further be processed without other processing.If desired, described polymkeric substance also can be handled with alkali, water-bearing media such as sodium hydroxide solution subsequently, but this is not preferred.
In the following example, except as otherwise noted, all have:
A) all consumptions are weight
B) all pressure are 0.10Mpa (definitely)
C) all temperature are 20 ℃.Embodiment
Institute all carries out under protective gas (argon gas) in steps.Used solvent is through the new distillatory of sodium/potassium-sodium alloy under protective gas.Used chemical particular sheet company/document is Cp a) 2ZrCl 2Merk, 8.03027.0005b) [FluCMe 2Cp] ZrCl 2J.A.Ewen, JACS (1988) 110,6255c) [FluSiMe 2Flu] ZrCl 2S.J.Palackal visits Yi Luote university degree paper, d in 1991) [F1u-C 2H 4-Flu] ZrCl 2S.J.Palackal visits Yi Luote university degree paper, e in 1991) [(2,6- iPr 2Ph) N=CH-CH=N WO-A-96/23010 (2,6- iPr 2Ph) NiBr 2F) trimethyl aluminium Merck, 8.14110.0150g) the organopolysiloxane particles embodiment 1 (adding entry as follows) that in EP-A-744432, mentions of Me-μ-gel:
2.0g Me-μ-gel is dissolved in the 250ml toluene, and 2 moles of toluene solutions of 30ml trimethyl aluminium (TMA) are added.This dispersion was at room temperature stirred 1 hour and be cooled to-78 ℃.Be added dropwise to 0.75ml water then lentamente.After gas is discharged fully, mixture was at room temperature stirred 4 hours, filter, with pentane washed twice and dry under high vacuum.Productive rate: the white solid that obtains 85% (based on the amount of TMA).Embodiment 2 (water adds with gaseous form):
2.0g Me-μ-gel is dissolved in the 250ml toluene, and 2 moles of toluene solutions of 30ml trimethyl aluminium (TMA) are added.This dispersion was at room temperature stirred 1 hour and be cooled to 40 ℃.Utilize the saturation steam form of argon that 0.75ml water is added in this dispersion then.After gas is discharged fully, mixture was at room temperature stirred 4 hours, filter, with pentane washed twice and dry under high vacuum.Productive rate: the white solid that obtains 100% (based on the amount of TMA).Embodiment 3 (olefinic polymerization):
Embodiment 1 and 2 solid can be used as heterogeneous cocatalyst., the white solid of 0.5g embodiment 1 and 2 is suspended in the 500ml pentane for this reason, and with 0.001mmol catalyst precursor (Cp 2ZrCl 2) toluene solution add.This suspension is used for polymerization (11 reactors, 10 crust ethylene pressures, 60 minutes, 60 ℃), (Al: Zr=300: 1).
Polymerization experiment:
Whether activity forms dirt
[kg PE/mmol h] embodiment 1 0.8 not embodiment 2 0.7 denys embodiment 4 (the not purified direct and catalyst precursor reaction of cocatalyst):
2.0g Me-μ-gel is dissolved in the 250ml toluene, and the 30ml toluene solution of 2 moles of trimethyl aluminiums (TMA) is added.This dispersion was at room temperature stirred 1 hour and be cooled to 40 ℃.Utilize the saturation steam form of argon gas that 0.75ml water is added in this dispersion then.After gas is discharged fully, mixture was at room temperature stirred 4 hours.The dichloride complex compound of 0.2mmol metallocene is added with the solid form and activate 30 minutes.Filter this mixture then, with pentane washed twice and dry under high vacuum.Productive rate: obtain 100% (based on the amount of TMA) solid, its dichloride complex compound according to metallocene has certain color.
The dichloride complex compound of used metallocene (Al: Zr=300: 1) be:
A) Cp 2ZrCl 2Cp=C 5H 5 IThe Pr=sec.-propyl
B) [FluCMe 2Cp] ZrCl 2Flu=C 13H 8The Ph=phenyl
c)[FluSiMe 2Flu]ZrCl 2
d)[Flu-C 2H 4-Flu]ZrCl 2
E) [(2,6- iPr 2Ph) N=CH-CH=N (2,6- iPr 2Ph) NiBr 2Embodiment 5 (using the olefinic polymerization of the catalyzer of preparation among the embodiment 4):
Olefinic polymerization is undertaken by the step that is similar to embodiment 3.
Polymerization result (11 reactors, ethylene pressure 10 crust, 60 minutes, 60 ℃):
Numbering active [kg PE/mmol h]
Embodiment 3, and a 1.0
Embodiment 3, and b 0.2
Embodiment 3, and c 1.5
Embodiment 3, and d 2.0
Embodiment 3, and e 0.1
In polymerization experiment, scale formation does not take place.Embodiment 6 (Comparative Examples: dried silica dioxide gel is as carrier):
The MAO solution of 30ml 30% (the weight % of toluene) is added into 3.0g in the silica dioxide gel of heating, drying, and said mixture was at room temperature stirred 4 hours.Then this mixture is filtered and with 25ml toluene and pentane washed twice.Drying obtains the 4.55g colourless powder under high vacuum.Embodiment 7 (Comparative Examples: aqueous silicon dioxide is as solid support material):
Trimethyl aluminium is added into 2.0g in the silica dioxide gel of heating, drying (Merck, water content about 7%), and said mixture was at room temperature stirred 4 hours.Then this mixture is filtered and with 25ml toluene and pentane washed twice.Drying obtains the 3.25g colourless powder under high vacuum.Embodiment 8 (using the olefinic polymerization of the cocatalyst system of preparation in embodiment 6 and 7):
This polymerization experiment is similar to the polymerization (11 reactors, 10 crust ethylene pressures, 60 minutes, 60 ℃) among the embodiment 3.
Catalyst precursor: Cp 2ZrCl 2
Embodiment A l: Zr activity [kg PE/ mmol ZrH]
8a??????????????????????7000∶1??????????????0.2
8b??????????????????????300∶1???????????????0
8c??????????????????????300∶????????????????0.02
Compare with embodiment 4, embodiment 8a and 8b show that with regard to the ratio of Al: Zr, the catalytic activity of novel cocatalyst is to be in a higher order of magnitude.Embodiment 9 (Comparative Examples):
1) preparation of resin:
209g (1mol) tetraethoxysilane and a kind of sily oxide or sily oxide or sily oxide mixture are mixed under room temperature in one 2 liters flask.The aqueous hydroxide solution of 51.3g water and 0.46g 20% is added in the said mixture.Flask is heated to 65 ℃ and kept this temperature 2 hours.Under 900 millibars, distill 115g ethanol then.150g toluene is added in the reaction soln, and uses sodium hydroxide that described solution is adjusted to neutrality.Then this reaction soln was kept 2 hours at 70 ℃.Then reaction soln is filtered out and solvent evaporation is fallen.In all cases, all obtain the powder that white dissolves in toluene with 2-3nm particle diameter.
Table 1:; MQ resin by method for preparing
Sample Sily oxide The mol ratio of M: Q Functional group
MQ1 88.6g hexamethyldisiloxane 0.5∶1 Methyl
MQ2 Hexamethyldisiloxane/tetramethyl divinyl disiloxane 0.6∶1 Methyl/vinyl
MQ3 Tetramethyl divinyl disiloxane 0.5∶1 Vinyl
MQ4 Tetramethyl disiloxane 0.45∶1 Hydrogen
2) preparation of fixed cocatalyst
Press embodiment 1 described preparation cocatalyst, obtain four sample CoMQ1, CoMQ2, CoMQ3 and CoMQ4.
3) press embodiment 4 described further processing sample CoMQ1, CoMQ2, CoMQ3 and CoMQ4.Here used catalyst precursor only is the complex compound 4a of embodiment 4.
4) polymerization of alkene is undertaken by being similar to embodiment 3.Gained active as shown in table 2.
Table 2:Al: the Zr ratio is 300: 1 a polymerization experiment
Cocatalyst Active [kg PE/mmol Zrh] Whether fouling
??CoMQ1 ????0.1 Not
??CoMQ2 ????0.2 Not
??CoMQ3 ????0.1 Not
??CoMQ4 ????0.02 A little
As can be seen from Table 2, with regard to comparable Al: with regard to the Zr ratio, compare with the activity that obtains of catalyzer 3a in embodiment 5, the activity of present embodiment be low 5-10 doubly.In addition, slight reactor fouling takes place under the situation of CoMQ4, just reactor wall is covered by the polyethylene layer of the about 1mm of thickness.

Claims (9)

1、一种含有具有5-200nm直径的有机聚硅氧烷凝胶微粒和固定在该微粒上的有机铝化合物的颗粒。CLAIMS 1. A particle comprising organopolysiloxane gel microparticles having a diameter of 5-200 nm and an organoaluminum compound immobilized on the microparticles. 2、如权利要求1所述的颗粒，其由[有机硅氧烷凝胶微粒部分]a[铝氧烷部分]b[单体和低聚有机铝化合物]c组成，其中，a为1-99.9wt.％，b为1-99wt.％且c为1-10wt.％，但个组分的加和为100wt.％。2. The particles according to claim 1, which are composed of [organosiloxane gel particle fraction] a [aluminoxane fraction] b [monomeric and oligomeric organoaluminum compound] c , wherein a is 1- 99.9wt.%, b is 1-99wt.% and c is 1-10wt.%, but the sum of the individual components is 100wt.%. 3、如权利要求2所述的颗粒，其中所述颗粒的有机聚硅氧烷部分由3. The particle of claim 2, wherein the organopolysiloxane portion of the particle is composed of 0.5-80wt.％的通式为[R1 dR2 3-dSiO1/2]    (1)的单元，0.5-80wt.% of the general formula is [R 1 d R 2 3-d SiO 1/2 ] (1) unit, 0-99.0wt.％的通式为[R1 eR2 2-eSi02/2]    (2)的单元，The general formula of 0-99.0wt.% is the unit of [R 1 e R 2 2-e Si0 2/2 ] (2), 0-99.5wt.％的通式为[R1 fR2 1-fSiO3/2]    (3)的单元和0-99.5wt.% of the general formula is [R 1 f R 2 1-f SiO 3/2 ] (3) units and 0-99.5wt.％的通式为[SiO4/2]    (4)的单元组成，The general formula of 0-99.5wt.% is the unit composition of [SiO 4/2 ] (4), 其中，R1是相同或不同的与Si-O-C-键连并选择性地含有官能团的单价C1-C30烃基或氢，Wherein, R 1 is the same or different monovalent C 1 -C 30 hydrocarbon groups or hydrogen bonded to Si-OC- and optionally containing functional groups, R2是相同或不同的与SiC-键连并选择性地含有官能团及还选择性由杂原子O，N或S间断的单价C1-C30烃基或氢，R 2 are identical or different monovalent C 1 -C 30 hydrocarbon radicals or hydrogen bonded to SiC- and optionally containing functional groups and optionally interrupted by heteroatoms O, N or S, d为0，1，2，3d is 0, 1, 2, 3 e为0，1或2，且e is 0, 1 or 2, and f为0或1。f is 0 or 1. 4、如权利要求2或3所述的颗粒，其中所述颗粒的铝氧烷部分由4. A particle as claimed in claim 2 or 3, wherein the aluminoxane portion of the particle consists of 0.5-99wt.％的通式为[XiR4 gR3 2-gAlO1/2]    (5)的单元，0.5-99wt.% of the general formula is [X i R 4 g R 3 2-g AlO 1/2 ] (5) units, 0-99wt.％的通式为[XjR4 hR3 1-hAlO2/2]    (6)的单元，和0-99 wt.% of units of the general formula [X j R 4 h R 3 1-h AlO 2/2 ] (6), and 0-99wt.％的通式为[AlO3/2]    (7)的单元组成，The general formula of 0-99wt.% is the unit composition of [AlO 3/2 ] (7), 其中，R3是一个氢原子，或相同或不同的与AlC-、SiC-键连并选择性地含有官能团的单价C1-C30烃基，Wherein, R 3 is a hydrogen atom, or the same or different monovalent C 1 -C 30 hydrocarbon groups bonded to AlC-, SiC- and optionally containing functional groups, R4是一个氢原子，或相同或不同的与Al-O-C-键连并选择性地含有官能团的单价C1-C30烃基，R 4 is a hydrogen atom, or the same or different monovalent C 1 -C 30 hydrocarbon groups bonded to Al-OC- and optionally containing functional groups, X是卤原子，X is a halogen atom, g为0，1或2，g is 0, 1 or 2, h为0或1，h is 0 or 1, i为0，1，2和3，且i is 0, 1, 2 and 3, and j为0，1或2。j is 0, 1 or 2. 5、如权利要求2-4所述的颗粒，其中所述单体有机铝化合物优选由下列通式5. Granules as claimed in claims 2-4, wherein the monomeric organoaluminum compound preferably consists of the general formula R3 3-i-jR4 i-jAlXj                             (8)，R 3 3-ij R 4 ij AlX j (8), R5 2AlYR5YR5                                (9)，R 5 2 AlYR 5 YR 5 (9), (CH2)5Al-YR5                               (10)，
Figure A9880859300031
的化合物组成，其中，R5是C1-C30烃基，(CH 2 ) 5 Al-YR 5 (10),
Figure A9880859300031
The composition of the compound, wherein, R 5 is C 1 -C 30 hydrocarbon group, Y是具有自由电子对的选自于氧、硫或NR6的基团，Y is a group selected from oxygen, sulfur or NR with a free electron pair, R6为一个氢原子或基团R5，R 6 is a hydrogen atom or a group R 5 , s为3至30的整数，和s is an integer from 3 to 30, and R3，R4，X，i和j如权利要求4定义。R 3 , R 4 , X, i and j are as defined in claim 4. 6、如权利要求2-5所述的颗粒，其中所述低聚有机铝化合物部分由通式6. Particles according to claims 2-5, wherein the oligomeric organoaluminum compound is partly represented by the general formula (R3AlO2/2)k(R4AlO2/2)1(XAlO2/2)m                 (13)，组成，其中，k，l和m分别为3-30的一个整数，且k+l+m之和至少为3，R3，R4，X，i和j如权利要求4定义。(R 3 AlO 2/2 ) k (R 4 AlO 2/2 ) 1 (XAlO 2/2 ) m (13), composition, wherein, k, l and m are respectively an integer of 3-30, and k+ The sum of l+m is at least 3, R 3 , R 4 , X, i and j are as defined in claim 4. 7、如权利要求2-5所述的颗粒，其中所述低聚线型有机铝化合物部分优选由通式(14)组成，R3 2-q-rR4 q-rXrAlO-(R3AlO2/2)n(R4AlO2/2)。7. Particles according to claims 2-5, wherein the oligomeric linear organoaluminum compound moiety preferably consists of the general formula (14), R 3 2-qr R 4 qr X r AlO-(R 3 AlO 2 /2 ) n (R 4 AlO 2/2 ).                                     (14)，(XAlO2/2)pAlR3 2-q-rR4 q-rXr (14), (XAlO 2/2 ) p AlR 3 2-qr R 4 qr X r 其中，n，o和p分别为0-50的一个整数，q和r分别为0，1和2，R3，R4和X如权利要求4中定义。Wherein, n, o and p are respectively an integer of 0-50, q and r are respectively 0, 1 and 2, R 3 , R 4 and X are as defined in claim 4. 8、一种制备如权利要求1-7所述颗粒的方法，其中将选自于上述通式(8)-(13)的化合物的有机铝化合物与带有羟基的化合物在具有5-200nm直径的有机聚硅氧烷凝胶微粒存在的情况下反应。8. A method for preparing particles as claimed in claims 1-7, wherein an organoaluminum compound selected from the compounds of the above-mentioned general formulas (8)-(13) and a compound having a hydroxyl group have a diameter of 5-200 nm React in the presence of organopolysiloxane gel particles. 9、如权利要求1-7所述的颗粒与周期表中IV、V、VI和VIII副族的金属化合物一起用作烯烃的低聚、环化或聚合的辅催化剂。9. Particles according to claims 1-7 as cocatalysts for the oligomerization, cyclization or polymerization of olefins together with metal compounds of subgroups IV, V, VI and VIII of the periodic table.
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US4925821A (en) * 1987-12-17 1990-05-15 Exxon Chemical Patents Inc. Method for utilizing triethyaluminum to prepare an alumoxane support for an active metallocene catalyst
US4945076A (en) * 1989-07-28 1990-07-31 Akzo America Inc. Polymerization catalyst system
US5206401A (en) 1990-06-08 1993-04-27 Akzo Chemicals Inc. Method of making alkylaluminoxane
US5633217A (en) * 1994-09-12 1997-05-27 Corning Incorporated Method of making a high strength catalyst, catalyst support or adsorber
DE19519446A1 (en) 1995-05-26 1996-11-28 Wacker Chemie Gmbh Monodisperse soluble organopolysiloxane particles
US5731253A (en) 1995-07-27 1998-03-24 Albemarle Corporation Hydrocarbylsilloxy - aluminoxane compositions
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